Treatment of hydrocarbons.



- besides,

UNITED STATES rA r nfr OFFICE.

EMILE AUGUSTE LEOPOLDE ROUXEVILLE,'OF PARIS, FRANCE.

TREATMENT OF HYDROCARB ONS.

Specification of Letters Patent.

Patented April 20, 1909.

Application filed June 11, 1906. Serial No. 321,297.

Paradis, Paris, France, have invented certam new and useful improvements in the Treatment of Hydrocarbons, with a view of obtaining an artificial product possessing most ofthe properties of india-ruhber and,

specification.

This invention relates to a process by means of which a great number of hydrocarbons may be changed in their composition so that an artificial product is formed,

which is distinguished by a new composition,

and new properties. This product is not soluble or less soluble in liquids, which dissolved the original hydrocarbons. The hydrocarbons which originally were liquid or viscous become more viscous or pasty and even solid; they no longer evaporate at ordinary temperature and are not acted upon by the substances which formerly did act upon them; the hydrocarbons which belong to the same class as the terpenes become plastic,

have. a tendency to become elastic and com bine dlrectly or indirectly with suliur, are

adapted to mix intimately with other artificial products or natural india rubber or become adapted to serve as dissolving medium or regenerator for natural" vulcanized india rubber and further they have insulating properties.

The products obtained according to the process, which forms the object of the pres- 5 ent invention, may also be utilized for the manufacture of varnish, bird-lime, glue, coating and for similar purposes if, for example the hydrocarbons are subjected only to a part of the process in question.

The product obtained by the entire process has greatsimilarity with natural india rubber and gutta-percha.

The process comprises three successive operations which according to the product to be obtained are either applied in totality or partially, each operation allowing modifications as for example the use of different chemical agents, aiming at the same effect. The operations composing the process are the followingz- 1. Transformation proper, which may be considered an oxidation or a polymerization and which is effected by submitting the hythe property of regenerating old? mdia-rubber, of which the following is a i drocarbon once or several times to the action of an oxidizing agent. This operation may be effected by heating or by cooling in'one operation or in several operations, by using the same oxidizing agent each time or by using dii'l'erent oxidizing agents.

2. Separation and purification of the new product. The same consists in eliminating 3' foreign bodies and the excess of the oxidizing agent. This operation may be carried out to a more or less high degree of perfection I either by washing with warm water and con- ;sequent decantation or by neutralization 1 new product in a suitable solvent, or by dis- 1 tilling the product under ordinary pressure or in cacao after having washed the same or finally by other chemical means.

3. Coagulation and vulcanization of the new product. These two operations are not indispensable. The same may be effected by the old means used for this purpose particularly with the aid of sulfur or of compounds of sulfur. These operations may be carried out immediately after the oxidizing operation. If liquid chlorid of sulfur is used F for this purpose it must be borne in mind that the presence of sulfur in the new product obtained may be useful or noxious according to the object aimed at.

When solid hydrocarbons such as resin or gums are to undergo the above transformation t-hcy are first powdered up and dissolved in spirit of turpentine or analogous hydrocarbons.

To better explain the process of transformation I shall hereinafter describe the application of the process to a well known mixture of hydrocarbons, for example, spirit of turpentine with the use of a distinct oxidizing agent viz,. sulfuric acid. It will be understood that by varying the proportions of l the two materials and according to whether j the mixing is done under cooling or without f cooling slightly different products will be lobtained. If operated under cooling, 100 l grains of spirit of turpentine are mixed with l 80 grams of sulfuric acid of Baum. If i one operates without cooling much less acid l is to be used but the reaction will be more violent and dillicult to effect without the formation of carbon, although it is possible when the operation is carried out slowly. The mixing of the two substances is effected in a very large vessel, which is externally cooled by flowing water or even with ice; if

and consequent washing or by dissolving the liO '10 -well carried out and when t e acid has been 7 in the latter instance the oxidation should not be suflicient it may be completed by slightly heating the combined materials. The mixtureis then left to cool for about 12 to 15 hours whereupon three quite distinct layers will have formed; the top-layer which is black and viscous, the intermediate part which is red and liquid and the bottom art whichis black. When theo erationhas een poured in very slowly and under continuous stirring lfhe'bottom part will be not very important. The three layers are. separated by decantation. The intermediate part, containing much acid and comparatively little hydrocarbon can be thrown away if one should not want to submit it to a separate treatment. The bottom part will be collected with a view to future utilization, as it contains useful viscous matter. The upper layer is then brought into anevaporator and heated with three or four times its volume of water to 80100 Gundercontinuous stir ring, whereupon it is allowed to settle until the product collects on the surface when it is separated by decantation. At thismoment the material may be submitted to distillation under ordinary pressure or in vacuo but this operation is not absolutely necessary. There could further be carried out at this moment the coagulation, which will be described subsequently. The roduct is then boiled in 4 to 5 times its vo ume of water to which an alkali is added, sodium hydrate or carbonate of sodium, the latter in preference; the alkali is added in sufiicient quantity to effect neutralization. To separate off the sodium salts the product is precipitated by any known chemical means for example by adding alum to the emulsion of the product in water, whereupon the solution is agitated and left to cool and settle. The product is then separated by decantation whereupon the product is washed repeatedly first in slightly acidulated warm water and then in pure warm water. The roduct may be utilized in'this state alrea y but it may be further oxidized which also could have been done after the separation of the upper layer for which pu1 ose it will be again treated either with su furic acid or with nitric acid, or with chlorid of sulfur. It must however be taken into consideration, that (1,) the use of azotic acid. gives a somewhat different product which is soluble in water and that (2) the action of the chlorid of sulfur not only effects an oxidation, but even a semivulcanization, which is advantageous for some roducts and disadvantageous for others because the product will contain sulfur which is difiicult to eliminate.

The refining can be obtained by dissolving the product in carbon bisulfid and in agitating the solution with very much water, which has to be renewed several times. The carbon bisulfid solution is separated from the cial substitutes used in the india rubber industry. Its principal use however consists in using it to regenerate vulcanized india.

rubber'as will be explained farther on. v A quick coagulation of the product may be obtained by adding to the new product obtained abou-tlO per cent. of its weight of carbon bisulfid, to make it more liquid if'necessary. llereupon about 10 per cent. of its weight of liquid chlorid of sulfur is added. After reaction, the solution is left to cool and settle; whereupon it is washed with boiling water, and, if required, part of thesulfur is eliminated by boiling the product in a con centrated solution of sodium hydrate ,whereby sulfid of sodium is roduced, which may easily be eliminated y successive washing with hot water. The chlorin may be removed with lime or in an other manner.

The vulcanization is e ected in the usual manner.

Byjudiciously varying the several operations and the proportions of the admixtures as-well as the degree of coagulation, artificial products may be obtained which are of compositions resembling those of the various natural india rubbers.

As already mentioned the product ob tained by the hereinbefore describedo eraations, may be used for regenerating vu canized india rubbers. canized loses certain qualities rincipally that of being soldered with itseli the rubber having been solidified partly b the vulcanization, is no longer viscous. To devulcanize this india rubber the sulfur must either be removed or that part be added which had imparted the viscosity to. the india rubber. The artificial product obtained by means of the present process possesses the following two articular properties: It has much afi inity or sulfur and further constitutes a perfect solvent for india rubber when it has been li uefied by heat. For these two reasons it is a apted to regencrate waste india rubber, because if mixed in suitable proportion with natural vulcanized india rubber and treated in a vulcanizing apparatus, after heating anew, a perfectly homogeneous product will be obtained, as an exchange of sulfur has taken place between the vulcanized india rubber and the artificial India rubber when vulproduct. The natural india rubber may be mixture with an alkali as the artificial prodnot combines with the alkali and afterward forms an emulsion in water.

As already mentioned the treatment as will and the novel product may be used for other purposes than those hereinbefore indicated without departing from the principle of the present invention.

What 1 claim as my invention and desire to secure by Letters Patent, is

1. The herein described process of treating hydrocarbons which consists in subjecting the latter to the action of sulfuric acid, cooling the mixture, separating the upper portion, heating the same with water, separating by decantation, boiling the product in an alkaline bath for neutralization, precipitating by means of alum, and refining the resultant product by subjecting it to carbon-bisulfid and eliminating the latter.

2. The herein described process of treating hydrocarbons which consists insubjeoting the latter to the action of sulfuric acid, cooling the mixture, separating the upper portion, heating the same with water, separating 1 by decantation, boiling the product in so-- well as the proportions of the chemicals used for the several operations may be varied at dium hydrate solution for neutralization, precipitating by means of alum, and refining the resultant product by subjecting it to carbon-bisulfid and eliminating the latter.

3. The herein described process of treating hydrocarbons which consists in submitting the latter to the action of an oxidizing agent, cooling the mixture, separating the upper i portion, heating the same with water, separating by decantation, boiling the product in sodium hydrate solution for neutralization,

precipitating by means of alum, and refining 2 the resultant product by subjecting it to carbon-bisultid and eliminating the latter.

In a itness whereof I have hereunto set my hand in presence of two witnesses.

EMILE AUGUS'IE LEOPOLDE ROUXEVILLE. Witnesses:

LUDWIG SARANDY, HANSON O. COKE. 

